CN108558887A - A kind of preparation method of the pyrrolo-pyrrole-dione organic material of end dye units substitution - Google Patents
A kind of preparation method of the pyrrolo-pyrrole-dione organic material of end dye units substitution Download PDFInfo
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- CN108558887A CN108558887A CN201810527629.XA CN201810527629A CN108558887A CN 108558887 A CN108558887 A CN 108558887A CN 201810527629 A CN201810527629 A CN 201810527629A CN 108558887 A CN108558887 A CN 108558887A
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- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
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Abstract
The present invention proposes a kind of preparation method of the pyrrolo-pyrrole-dione organic material of end dye units substitution, using thienyl pyrrolo-pyrrole-dione dialdehyde and 3 ethyl rhodanines as raw material, dropwise addition organic amine makees catalyst after a certain amount of solvent is added, reaction a period of time at a certain temperature, it washs after reaction, is dry, removing solvent, crude product is recrystallized to give target product.The advantage of the invention is that making solvent instead of chloroform with the dichloromethane of low toxicity, the problem that controlled drug is purchased and processing is complicated is avoided；The present invention condition can carry out at room temperature, energy consumption is reduced compared with the heated reflux condition having disclosed, energy conservation and environmental protection, safety coefficient are high, equipment is simple and convenient to operate, reaction system does not need the specially treateds such as anhydrous and oxygen-free, harsh reaction condition is avoided, large-scale production and industrial applications are suitble to.
Description
Technical field
The present invention relates to a kind of organic conjugate small molecules to synthesize field, is related to a kind of pyrroles of end dye units substitution
And the preparation method of pyrroledione organic material.
Background technology
Organic photoelectrical material has pi-conjugated molecular structure and excellent electron delocalization performance, diversified structure composition
With property regulation space, the different photo absorption performances that material is adjusted to the combination of receptor unit, optical band gap, track energy can be passed through
Grade etc., to be widely used in Organic Light Emitting Diode, the fields such as field-effect transistor and solar cell.Dye units
Pyrrolo-pyrrole-dione（Diketopyrrolopyrrole, DPP）Molecular skeleton has gay colours and excellent stability
And receive extensive attention, and DPP skeletons can pass through the optical absorption properties and rail of different end modified adjusting materials
Road energy level.It is used as organic solar batteries donor material as oligo-thiophenes are connected to the both ends DPP structure compound SMD1 by Nguyen
Material（Applied Physics Letters, 2008, 93, 163306）.And Langa is by dye groups rhodanine
（Rhodanine, RD）Modification the both sides DPP build battery acceptor material MPU1, the compound due to dye groups introducing and
The electric charge transfer collective effect of intramolecular shows strong visible absorption property and relatively narrow optical band gap, obtains higher light
Photoelectric transformation efficiency（Acs. Appl. Mater. Inter.2017, 9, 11739,Journal of Industrial and Engineering Chemistry2017, 45, 338）.It is an electrons and holes mobility that Wang, which also reports DPPT-RH,
Compared with the bipolarity organic semiconducting materials of balance（Acs. Appl. Mater. Inter.2017, 9, 14967）.This is fully demonstrate,proved
The bright end dye groups modification based on DPP skeletons can obtain the multi-functional organic photoelectrical material haveing excellent performance, therefore such
The synthesis of compound causes people widely to pay close attention to.
The preparation method of the pyrrolo-pyrrole-dione organic material for the end dye units substitution enumerated in above-mentioned document is
It is prepared by Knoevenagel condensation reactions by the dialdehyde and corresponding dye groups of DPP, in chloroform and piperidines or chloroform or three
The in the mixed solvent of ethamine is heated to reflux to obtain target product.Chloroform and piperidines belong to high poison chemicals, and wherein chloroform also belongs to
In easy drugs processed, skin, oral mucosa, respiratory apparatus and eyes may be stimulated by making solvent, aoxidized by the oxygen in air and
Generating has the phosgene of severe toxicity, has narcoticness and carcinogenicity to belong to the reagent by public security department's control, therefore have using chloroform solvent
Larger harm.And similar preparation reaction is required to the atmosphere for making system be heated to reflux and being maintained at inert gas, and it is difficult
To be produced on a large scale.Therefore be badly in need of exploring the simple, convenient of the DPP organic materials of this kind of end dye units substitution and
Efficient preparation method is conducive to production and application.
Invention content
To solve the above problems, the present invention proposes a kind of pyrrolo-pyrrole-dione organic material of end dye units substitution
Preparation method, it is characterised in that：A certain amount of compound 1 and 3- ethyl rhodanines, are added dropwise after the solvent of certain volume is added
Organic amine makees catalyst, after reacting a period of time at a certain temperature, system is washed with water three times, organic phase is through anhydrous
MgSO4Solvent is removed after drying, is obtained target product after crude product recrystallization, is reacted as shown in formula one：
Formula one
Compound 1 of the present invention and the molar ratio of 3- ethyl rhodanines are 1：5~1：20, wherein it is preferred that 1：10.
Organic solvent of the present invention is dichloromethane, chlorobenzene and N,N-dimethylformamide（DMF）In one kind, wherein
It is preferred that dichloromethane, every 0.1 mmol compounds 1 need 1 mL of solvent.
Organic amine in synthetic method of the present invention is piperidines, triethylamine and 1,11 carbon -7- alkene of 8- diazabicylos,
Wherein preferred triethylamine, compound 1 are 1 with organic amine molar ratio：10.
Reaction time in synthetic method of the present invention is 2~12 hours.
Temperature of the present invention is 25~80oC。
Solvent used in recrystallization of the present invention is volume ratio 20：1 dichloromethane and the mixed solution of methanol.
Compared with the synthetic method for disclosing report, the present invention proposes a kind of pyrrolopyrrole of end dye units substitution
The preparation method of diketone organic material is low using toxicity, price is relatively low, the dichloromethane that derives from a wealth of sources makees solvent and replaces three chloromethanes
Alkane avoids the problem of expensive, the higher controlled drug chloroform buying of toxicity and post-processing complexity；The present invention is in room temperature
Under the conditions of carry out, energy consumption, energy conservation and environmental protection, safety coefficient are significantly reduced compared with the heated reflux condition for having disclosed report
Height, equipment is simple, easy to operate, avoids harsh reaction condition, is suitble to large-scale production and industrial applications.
Description of the drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of molecule；
Fig. 2 is the high resolution mass spectrum figure of molecule.
Specific implementation mode
In order to make the present invention technological means be easier to understand, be further described below with reference to specific embodiment, but
The implementation of the present invention is not limited to this.
Embodiment 1
With molar ratio for 1 in 50 mL round-bottomed flasks：5 are added compound 1（0.2 mmol, 116 mg）With 3- ethyl rhodanines
（1.0 mmol, 161 mg）, the triethylamine of 20 mL dichloromethane and 0.02 mmol is added, keeps room temperature reaction 10 hours, instead
System is washed with water three times after answering, organic phase is through anhydrous MgSO4Solvent is removed after drying, crude product is with volume ratio
20：1 dichloromethane and methanol solution is recrystallized to give violet solid powdered product, yield 65%.
Embodiment 2
With molar ratio for 1 in 50 mL round-bottomed flasks：10 are added compound 1（0.2 mmol, 116 mg）With 3- ethyl rhodanines
（2.0 mmol, 322 mg）, the triethylamine of 20 mL dichloromethane and 0.02 mmol is added, keeps room temperature reaction 10 hours, instead
System is washed with water three times after answering, organic phase is through anhydrous MgSO4Solvent is removed after drying, crude product is with volume ratio
20：1 dichloromethane and methanol solution is recrystallized to give violet solid powdered product, yield 87%.
Embodiment 3
With molar ratio for 1 in 50 mL round-bottomed flasks：20 are added compound 1（0.2 mmol, 116 mg）With 3- ethyl rhodanines
（4.0 mmol, 644 mg）, the triethylamine of 20 mL dichloromethane and 0.02 mmol is added, keeps room temperature reaction 10 hours, instead
System is washed with water three times after answering, organic phase is through anhydrous MgSO4Solvent is removed after drying, crude product is with volume ratio
20：1 dichloromethane and methanol solution is recrystallized to give violet solid powdered product, yield 90%.
Embodiment 4
With molar ratio for 1 in 50 mL round-bottomed flasks：10 are added compound 1（0.2 mmol, 116 mg）With 3- ethyl rhodanines
（2.0 mmol, 322 mg）, the triethylamine of 20 mL chlorobenzenes and 0.02 mmol is added, keeps room temperature reaction 10 hours, reaction knot
System is washed with water three times after beam, organic phase is through anhydrous MgSO4Solvent is removed after drying, crude product volume ratio is 20：1
Dichloromethane and methanol solution are recrystallized to give violet solid powdered product, yield 51%.
Embodiment 5
With molar ratio for 1 in 50 mL round-bottomed flasks：10 are added compound 1（0.2 mmol, 116 mg）With 3- ethyl rhodanines
（2.0 mmol, 322 mg）, the triethylamine of 20 mL DMF and 0.02 mmol is added, keeps room temperature reaction 10 hours, reaction knot
System is washed with water three times after beam, organic phase is through anhydrous MgSO4Solvent is removed after drying, crude product volume ratio is 20：1
Dichloromethane and methanol solution are recrystallized to give violet solid powdered product, yield 61%.
Embodiment 6
With molar ratio for 1 in 50 mL round-bottomed flasks：10 are added compound 1（0.2 mmol, 116 mg）With 3- ethyl rhodanines
（2.0 mmol, 322 mg）, the piperidines of 20 mL dichloromethane and 0.02 mmol is added, keeps room temperature reaction 10 hours, reaction
After system is washed with water three times, organic phase is through anhydrous MgSO4Solvent is removed after drying, crude product volume ratio is 20：1
Dichloromethane and methanol solution be recrystallized to give violet solid powdered product, yield 68%.
Embodiment 7
With molar ratio for 1 in 50 mL round-bottomed flasks：10 are added compound 1（0.2 mmol, 116 mg）With 3- ethyl rhodanines
（2.0 mmol, 322 mg）, the DBU of 20 mL dichloromethane and 0.02 mmol is added, keeps room temperature reaction 10 hours, reaction knot
System is washed with water three times after beam, organic phase is through anhydrous MgSO4Solvent is removed after drying, crude product volume ratio is 20：1
Dichloromethane and methanol solution are recrystallized to give violet solid powdered product, yield 88%.
Embodiment 8
With molar ratio for 1 in 50 mL round-bottomed flasks：10 are added compound 1（0.2 mmol, 116 mg）With 3- ethyl rhodanines
（2.0 mmol, 322 mg）, the triethylamine of 20 mL dichloromethane and 0.02 mmol is added, keeps 40oC reactions 4 hours, instead
System is washed with water three times after answering, organic phase is through anhydrous MgSO4Solvent is removed after drying, crude product is with volume ratio
20：1 dichloromethane and methanol solution is recrystallized to give violet solid powdered product, yield 91%.
Embodiment 9
With molar ratio for 1 in 50 mL round-bottomed flasks：10 are added compound 1（0.2 mmol, 116 mg）With 3- ethyl rhodanines
（2.0 mmol, 322 mg）, the triethylamine of 20 mL chlorobenzenes and 0.02 mmol is added, keeps 60oC reacts 10 hours, reaction knot
System is washed with water three times after beam, organic phase is through anhydrous MgSO4Solvent is removed after drying, crude product volume ratio is 20：1
Dichloromethane and methanol solution are recrystallized to give violet solid powdered product, yield 62%.
Embodiment 10
With molar ratio for 1 in 50 mL round-bottomed flasks：10 are added compound 1（0.2 mmol, 116 mg）With 3- ethyl rhodanines
（2.0 mmol, 322 mg）, the triethylamine of 20 mL chlorobenzenes and 0.02 mmol is added, keeps 80oC reacts 10 hours, reaction knot
System is washed with water three times after beam, organic phase is through anhydrous MgSO4Solvent is removed after drying, crude product volume ratio is 20：1
Dichloromethane and methanol solution are recrystallized to give violet solid powdered product, yield 64%.
Embodiment 11
With molar ratio for 1 in 50 mL round-bottomed flasks：10 are added compound 1（0.2 mmol, 116 mg）With 3- ethyl rhodanines
（2.0 mmol, 322 mg）, the triethylamine of 20 mL dichloromethane and 0.02 mmol is added, keeps room temperature reaction 2 hours, reaction
After system is washed with water three times, organic phase is through anhydrous MgSO4Solvent is removed after drying, crude product volume ratio is 20：1
Dichloromethane and methanol solution be recrystallized to give violet solid powdered product, yield 35%.
Embodiment 12
With molar ratio for 1 in 50 mL round-bottomed flasks：10 are added compound 1（0.2 mmol, 116 mg）With 3- ethyl rhodanines
（2.0 mmol, 322 mg）, the triethylamine of 20 mL dichloromethane and 0.02 mmol is added, keeps room temperature reaction 12 hours, instead
System is washed with water three times after answering, organic phase is through anhydrous MgSO4Solvent is removed after drying, crude product is with volume ratio
20：1 dichloromethane and methanol solution is recrystallized to give violet solid powdered product, yield 89%.
Claims (6)
1. a kind of preparation method of the pyrrolo-pyrrole-dione organic material of end dye units substitution, it is characterised in that：Centainly
The compound 1 and 3- ethyl rhodanines of amount, dropwise addition organic amine makees catalyst after the solvent of certain volume is added, in certain temperature
After lower reaction a period of time, system is washed with water three times, organic phase is through anhydrous MgSO4Solvent, crude product weight are removed after drying
Target product is obtained after crystallization, is reacted as shown in formula one：
Formula one
A kind of preparation method of the pyrrolo-pyrrole-dione organic material of end dye units substitution according to claim 1,
It is characterized in that：The compound 1 and the molar ratio of 3- ethyl rhodanines are 1：5~1：20, wherein it is preferred that 1：10.
2. a kind of preparation side of the pyrrolo-pyrrole-dione organic material of end dye units substitution according to claim 1
Method, it is characterised in that：The solvent is one kind in dichloromethane, chlorobenzene and n,N-Dimethylformamide, wherein it is preferred that dichloro
Methane, dosage are that every 0.1 mmol compounds 1 need 1 mL of solvent.
3. a kind of preparation side of the pyrrolo-pyrrole-dione organic material of end dye units substitution according to claim 1
Method, it is characterised in that：Organic amine as catalyst be piperidines, triethylamine and 1,11 carbon -7- alkene of 8- diazabicylos, wherein
It is preferred that triethylamine, compound 1 is 1 with organic amine molar ratio：10.
4. a kind of preparation side of the pyrrolo-pyrrole-dione organic material of end dye units substitution according to claim 1
Method, it is characterised in that：Reaction time in the synthetic method is 2~12 hours.
5. a kind of preparation side of the pyrrolo-pyrrole-dione organic material of end dye units substitution according to claim 1
Method, it is characterised in that：Temperature is 25~80 in the synthetic methodoC。
6. a kind of preparation side of the pyrrolo-pyrrole-dione organic material of end dye units substitution according to claim 1
Method, it is characterised in that：It is volume ratio 20 that solvent used is recrystallized in the synthetic method：1 dichloromethane and methanol it is mixed
Close solution.
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Citations (8)
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|---|---|---|---|---|
| JPS6257465A (en) * | 1985-09-06 | 1987-03-13 | Fuji Photo Film Co Ltd | Novel methine dye |
| US4965155A (en) * | 1987-12-03 | 1990-10-23 | Mita Industrial Co., Ltd. | Organic photoconductive material for electrophotography |
| WO2006047269A2 (en) * | 2004-10-22 | 2006-05-04 | Exelixis, Inc. | Pharmaceutical compositions |
| CN1962621A (en) * | 2005-11-09 | 2007-05-16 | 北京大学 | Organic semiconductor compound and its preparation method and uses |
| JP2012214738A (en) * | 2011-03-30 | 2012-11-08 | Hodogaya Chem Co Ltd | Sensitizing dye for photoelectric conversion, photoelectric conversion element using the same, and dye-sensitized solar cell |
| CN104130252A (en) * | 2014-07-15 | 2014-11-05 | 南开大学 | Organic photoelectric compound as well as preparation method and application thereof |
| CN104774200A (en) * | 2014-01-09 | 2015-07-15 | 南开大学 | Preparation of organic photoelectric material |
| CN107793435A (en) * | 2016-08-29 | 2018-03-13 | 中国科学院化学研究所 | One kind conjugation organic molecule solar cell acceptor material compound and preparation method and application |
-
2018
- 2018-05-29 CN CN201810527629.XA patent/CN108558887A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6257465A (en) * | 1985-09-06 | 1987-03-13 | Fuji Photo Film Co Ltd | Novel methine dye |
| US4965155A (en) * | 1987-12-03 | 1990-10-23 | Mita Industrial Co., Ltd. | Organic photoconductive material for electrophotography |
| WO2006047269A2 (en) * | 2004-10-22 | 2006-05-04 | Exelixis, Inc. | Pharmaceutical compositions |
| CN1962621A (en) * | 2005-11-09 | 2007-05-16 | 北京大学 | Organic semiconductor compound and its preparation method and uses |
| JP2012214738A (en) * | 2011-03-30 | 2012-11-08 | Hodogaya Chem Co Ltd | Sensitizing dye for photoelectric conversion, photoelectric conversion element using the same, and dye-sensitized solar cell |
| CN104774200A (en) * | 2014-01-09 | 2015-07-15 | 南开大学 | Preparation of organic photoelectric material |
| CN104130252A (en) * | 2014-07-15 | 2014-11-05 | 南开大学 | Organic photoelectric compound as well as preparation method and application thereof |
| CN107793435A (en) * | 2016-08-29 | 2018-03-13 | 中国科学院化学研究所 | One kind conjugation organic molecule solar cell acceptor material compound and preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| SAN-LIEN WU,ET AL.: "Roles of 3‑Ethylrhodanine in Attaining Highly Ordered Crystal Arrays of Ambipolar Diketopyrrolopyrrole Oligomers", 《ACS APPL. MATER. INTERFACES》 * |
| 中华人民共和国卫生部 发布: "《有机溶剂作业场所 个人职业病防护用品使用规范》", 29 February 2008, 人民卫生出版社 * |
| 王进军 等: "焦脱镁叶绿酸的Knoevenagel 反应及其杂环取代衍生物的合成", 《有机化学》 * |
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Application publication date: 20180921 |